CeO2 has been used as heterogeneous catalyst for carbon‐carbon bond formation via cross‐dehydrogenative coupling (CDC). It works efficiently for oxidative C−C bond formation between N‐aryltetrahydroisoquinoline derivatives and a carbon nucleophile nitroalkane and acetone under aerobic conditions. This is the first report of CeO2 as a low temperature catalyst for the carbon‐carbon bond formation reaction between two sp3 C−H bonds.

A novel heterogeneous catalytic hydrogenation-hydrogenolysis strategy has been developed for the α-methylation of ketones via enaminones using DMF dimethyl acetal as carbon source. This strategy provides a very convenient route to α-methylated ketones using a variety of ketones without any base or oxidant.

A palladium catalyzed cascade reaction of 4-hydroxycoumarins and in situ generated arynes has been developed for the direct synthesis of coumestans. This cascade strategy proceeds via C-H bond activation/C-O and C-C bond formations in a single reaction vessel. This methodology affords moderate to good yields of coumestans and is tolerant of a variety of functional groups including halide. The methodology was applied to the synthesis of natural product flemichapparin C.

A transition-metal-free coupling reaction of aryne, DMSO, and activated alkyne for the synthesis of 2-[(o-methylthio)­aryloxy]-substituted dialkyl maleates is reported. This cascade process is associated with several bond cleavage as well as bond formation reactions in one pot. One of our synthesized maleates has been unambiguously established by single-crystal XRD studies. This methodology allows preparation of trisubstituted vinyl ethers with excellent stereospecificity.